US20070006529A1 - Compact steam reformer - Google Patents

Compact steam reformer Download PDF

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US20070006529A1
US20070006529A1 US11/514,537 US51453706A US2007006529A1 US 20070006529 A1 US20070006529 A1 US 20070006529A1 US 51453706 A US51453706 A US 51453706A US 2007006529 A1 US2007006529 A1 US 2007006529A1
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evaporator
reactor
steam reformer
follow
pipe
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Joachim Wunning
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WS-REFORMER GmbH
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    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J8/0496Heating or cooling the reactor
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    • B01J8/0415Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds the beds being superimposed one above the other
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    • B01J8/0446Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0461Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds
    • B01J8/0469Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds the beds being superimposed one above the other
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0492Feeding reactive fluids
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00026Controlling or regulating the heat exchange system
    • B01J2208/00035Controlling or regulating the heat exchange system involving measured parameters
    • B01J2208/00044Temperature measurement
    • B01J2208/00061Temperature measurement of the reactants
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00115Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/00132Tubes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00115Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/00141Coils
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00168Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00194Tubes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00168Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00203Coils
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00309Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00477Controlling the temperature by thermal insulation means
    • B01J2208/00495Controlling the temperature by thermal insulation means using insulating materials or refractories
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00504Controlling the temperature by means of a burner
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/0053Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00539Pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00716Means for reactor start-up
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the invention relates to a compact steam reformer and a method for steam reformation.
  • a compact steam reformer is known from DE 101 19 083 A1, in which the process water is essentially evaporated by means of the reformate to be cooled. The waste heat from the combustion is recovered by pre-warming the air. NOx formation is avoided by employing the flameless oxidation process.
  • This reformer permits a rapid output regulation and has a degree of effectiveness of up to approximately 80%.
  • the novel compact steam reformer ( 1 ) combines in one device the steam reformation of natural gas or other fuel, including subsequent cleaning of CO. Controlled catalytic CO cleaning is achieved by careful temperature control at the follow-up reactor ( 37 , 39 , 39 a ). Temperature control is made possible by means of pressure-controlled operation of the evaporator ( 24 ).
  • the compact steam reformer in accordance with the invention has a reactor which is heated by means of a burner.
  • a preheating device with a high rate of heat recovery is assigned to the burner. This increases the efficiency of the reforming process.
  • the reformer furthermore has a follow-up reactor, which is designed for performing a shift reaction, follow-up oxidation and/or methane generation from the carbon monoxide portions contained in the raw reformate.
  • the follow-up reactor is in a heat-exchanging connection with a pipe evaporator, which maintains the temperature of the follow-up reactor at a fixed level in a controlled manner. By means of this, the desired selectivity of the follow-up reaction is maintained, even in case of a load change.
  • the pipe evaporator causes the evening-out of the temperature in the follow-up reactor in regard to time, as well as in regard to space.
  • the flow of material in the pipe evaporator causes a heat transport in the follow-up reactor, so that the latter can be rapidly adapted to a load change. This applies in particular if the pipe evaporator and the follow-up reactor operate in accordance with a co-current flow.
  • the temperature of the follow-up reactor is simultaneously fixed within such narrow limits that the CO content can be reduced to values of less than 50 ppm. Because of this, catalytic follow-up treatment, filtering or other follow-up treatment of the process gas becomes superfluous.
  • the gas generated by the compact steam reformer can be directly conducted to hydrogen fuel cells.
  • the temperature of the follow-up reactor can be set in the simplest way by the regulation of the steam pressure.
  • the steam generation temperature for all operational states is simultaneously fixed, along with the steam pressure.
  • the close thermal connection between the follow-up reactor and the pressure-regulated evaporator for example by means of the embodiment of the pipe evaporator as a pipe coil and the arrangement of possible catalyzers in the spaces between the pipes, creates favorable conditions for the generation of low-CO hydrogen.
  • the compact steam reformer can have a jet pump connected to the pipe evaporator or other evaporator, which generates a fuel—steam mixture of a preselected composition and feeds the reactor.
  • a jet pump connected to the pipe evaporator or other evaporator, which generates a fuel—steam mixture of a preselected composition and feeds the reactor.
  • This provides the basis for a particularly simple control of the compact steam reformer by means of control techniques.
  • the amount of steam is controlled by an appropriate metering of feed water amounts.
  • the amount of fuel supplied to the reformer for reforming need not be separately controlled and is instead metered in by the jet pump.
  • FIG. 1 is a compact steam reformer with an attached fuel cell in a schematic representation
  • FIG. 2 is the temperature profile of the process gases in the form of a diagram
  • FIG. 3 is the temperature profile of the heating gases in the form of a diagram
  • FIG. 4 is the compact steam reformer in schematic longitudinal section with the allocation of its work zones to the diagrams in accordance with FIGS. 2 and 3 .
  • a steam reformer 1 is represented in longitudinal section in FIG. 1 . It has an outer shell 2 of a length L and circular cross section of a diameter D. It can be cylindrical, or also stepped in the form of several cylinders. All connectors 3 are preferably conducted through its upper end 4 .
  • a reformer pipe 5 closed at the bottom, is arranged concentrically inside the shell 2 and at a distance from it.
  • the annular space provided between the shell 2 and the reformer pipe 5 is filled with an insulating material 6 for thermal insulation.
  • a feed line 7 for a mixture of fuel and steam leads from the upper end 4 , extending initially straight and then downward by means of turns through the insulating material 6 to a feed connector 8 at the lower end of the reformer pipe 5 .
  • the lower, cup-shaped end of the latter constitutes the outer shell of a reactor 9 for performing the actual reforming process.
  • the reactor 9 is delimited by an inner reformer pipe 11 , which is closed off in a cup shape at the bottom and is maintained on the end 4 at the top.
  • a catalyzer 12 for the reforming process is arranged in the cup-shaped annular space between the lower end of the inner reformer pipe 11 and the lower end of the outer reformer pipe 5 .
  • the reformer pipe 11 is provided with ribs 13 , 14 on the inside as well as on the outside, which are used for heat transfer between the catalyzer 12 and a combustion chamber 15 , which is enclosed by the reformer pipe 11 .
  • a burner 16 is assigned to the combustion chamber and is used for heating the catalyzer 12 and is designed to create a flameless oxidation of the fuel introduced into the combustion chamber 15 .
  • a number of gas and air nozzles 17 , 18 is provided for this purpose, which are arranged, aligned in the same direction, in a ring and create a large-volume circulation.
  • a hollow-cylindrical guide body 19 which is arranged concentrically with the ring of nozzles can assist the large-volume circulation, which is indicated by arrows in FIG. 1 .
  • the gas nozzles 17 are fed via a preheating arrangement 20 , which utilizes waste heat. Parts of this are lines 21 , 22 , which are conducted in the form of coils through an exhaust gas conduit 23 formed inside the upper part of the reformer pipe 11 . In this way the combustion gas supplied to the combustion chamber 15 , as well as the supplied air, are preheated. A high recouperation degree, and therefore cool exhaust gas, is achieved.
  • An ignition burner Z or an electric heating device can be centrally provided, which are used for preheating the combustion chamber 15 until the start of the flameless oxidation.
  • the steam reformer 1 so far described contains a steam generator 24 arranged in the annular space 10 between the outer recouperation pipe 5 and the inner recouperation pipe 11 and is coupled with them in a heat-technological manner.
  • the steam generator 24 is constituted by a pipe coil, which is divided into several sections and is arranged concentrically in respect to the preheating device.
  • a pipe 25 is arranged in-between, which encloses a further annular space 26 together with the inner reformer pipe 11 .
  • This space is filled with an insulating material 27 for the thermal insulation of the exhaust gas conduit 23 from the reformate conduit, which is formed between the outer reformer pipe 5 and the pipe 25 through the annular space 10 .
  • the steam generator 24 has a feedwater connector 28 , starting from which a first pipe coil section 29 leads through the reformate conduit, which terminates at a reformate outlet 31 .
  • the pipe coil section 29 constitutes a water/reformate counterflow radiator operating in a counterflow manner.
  • the pipe coil 29 leads to a bridging pipe 32 , which leads through the space 26 in the axial direction. It then changes back into the outer annular space 10 constituting the reformat conduit, and is continued there as the pipe coil section 33 . It constitutes a water heater and simultaneously a reformate shock cooler (quench cooler, section A in FIGS. 3 and 5 ).
  • a gas-permeable annular insulating body 34 is arranged between the pipe coil section 33 and the catalyzer 12 , which prevents overheating of the steam generator 24 when there is no load, i.e. in case of a feedwater flow-through of zero or close to zero.
  • a further pipe coil section 35 follows the pipe coil section 33 and consists of several coils 36 , 38 (section B in FIGS. 3 and 5 ). These coils 36 , 38 have been embedded in a catalyzer, which also fills spaces between coils and constitutes a follow-up reactor.
  • the first coils 36 have been embedded, for example, in a CO-shift catalyzer 37 .
  • the subsequent coils 38 (section C in FIGS. 3 and 5 ) have been embedded in a methane-generating catalyst 39 .
  • the catalysts 37 , 39 can be attached to a suitable catalyst body, such as a woven wire device or the like, for example, or also deposited as loose bulk material between the coils 36 , 38 , or can be directly formed on the ribs of an evaporator embodied as a ribbed pipe.
  • a suitable catalyst body such as a woven wire device or the like, for example, or also deposited as loose bulk material between the coils 36 , 38 , or can be directly formed on the ribs of an evaporator embodied as a ribbed pipe.
  • the evaporator 24 is divided into three sections A, B, C, namely the pipe coil section 33 for the at least partial evaporation of the water and shock cooling of the reformats, as well as the sections constituted by the coils 36 and 38 , in which the further, to a large extent complete evaporation of the water is provided by heat exchange with the respective catalyzers 37 , 39 .
  • the catalysts 37 , 39 constitute the two-stage follow-up reactor.
  • the outlet of the evaporator 24 is connected via an ascending pipe 41 with a pressure-control valve 42 , which maintains the pressure in the evaporator 24 constant, regardless of the flow through it.
  • the steam emitted by the pressure-control valve 42 is conducted to the propellant nozzle connector 43 of a jet pump 44 , whose suction connector 45 is connected to a fuel feed line. Its outlet feeds a mixture of steam and fuel to the feed line 7 .
  • the feedwater connector 28 is provided with feedwater by a feedwater pump 46 .
  • the latter is controlled or regulated by a control device 47 on the basis of a temperature of the catalyzer 12 detected by means of a temperature sensor 48 in such a way, that the temperature of the catalyzer 12 is kept constant. Since the air requirement for the burner and the fuel cell are proportional to the energy supply PCH4, and therefore the feedwater temperature, the regulation ratio of the air blower 49 can track in a simple manner the regulation ratio of the feedwater pump 46 , which is specified by the control device 47 .
  • Air and combustion gas are supplied via the lines 21 , 22 .
  • the residue gas from the anode of a fuel cell can be used as the combustion gas.
  • the reformate is conducted to an anode input of a fuel cell 52 .
  • Residue gas generated by the anode is conducted via a line 53 to the preheating arrangement 20 .
  • the blower 49 conveys air to the cathode of the fuel cell and to the preheating arrangement 20 .
  • FIG. 3 illustrates the temperature of the gases supplied via the lines 21 , 22 , namely air and combustion gas.
  • the branch II of the curve illustrates the exhaust gas temperature of the exhaust gas conducted out in counterflow.
  • the represented temperatures reflect the temperature profile in the steam reformer 1 illustrated in FIG. 4 , in particular in its recouperator.
  • the loop-shaped branch III of the curve in FIG. 3 represents the temperature in the combustion chamber 15 in the course of the flameless oxidation. As represented, the gas performs several revolutions through the combustion chamber 15 .
  • an exhaust gas temperature of, for example, 150° C., to attain an air and gas preheating up to approximately 800° C.
  • the curve in FIG. 2 represents the temperature profile of the gas to be reformed and already reformed.
  • the branch IV of the curve indicates the heating of the feedwater in the pipe coil section 29 , which is simultaneously a feedwater preheater and a water reformate counterflow cooler.
  • the feedwater which is under pressure and preheated, is conducted to the evaporator 24 at a temperature of slightly above 100° C. Initially, this is symbolized by the lower horizontal branch V of the curve.
  • the preheated feedwater enters the evaporator at a point VI. It is brought to the evaporation temperature (curve VIII) in the pipe coil section 33 , and then passes through the entire evaporator 24 , in which it slowly evaporates.
  • the pipe evaporator 24 sets a uniform temperature for the follow-up reactor.
  • the evaporation temperature T s is not exceeded.
  • the size of the evaporator temperature is set by means of the evaporator pressure at the pressure-control valve 42 .
  • the temperature profile in accordance with FIG. 2 is also maintained within narrow limits, even in case of load changes, in particular in the last stage.
  • the selectivity of the follow-up reaction is maintained in this way.
  • the temperature setting in the last follow-up reactor stage is here effected solely by pressure control.
  • the generated steam reaches the jet pump 44 .
  • the latter fixes the steam/fuel ratio by means of its ratio between the propellant nozzle diameter and the mixing nozzle diameter.
  • the jet pump 44 aspirates the desired amount of fuel via its suction connector 45 and mixes it with steam.
  • the steam temperature initially slightly drops ( FIG. 2 , branch XI of the curve), wherein the temperature of the admixed combustion gas suddenly rises (branch X of the curve). Then the temperature slowly rises until the feed connector 8 is reached (branch XI of the curve).
  • the temperature of the curve continues to increase in accordance with the branch XII until it reaches the temperature T R , which has been detected by the temperature sensor 49 and is constantly regulated by metering in feedwater.
  • the reformate generated by the catalyzer 12 leaves the reactor 9 at this temperature.
  • the reformate is shock-cooled ( FIG. 2 , branch XIII of the curve) as section A.
  • the steam reformer 1 so far described operates inherently stably.
  • An increased reduction of the electrical output Pe 1 worsens the caloric value of the residue gas from the anode.
  • the control device increases the feedwater conveyance and therefore the steam generation and the reformate generation.
  • the resultant increase of residue gas from the anode increases the burner output in the combustion chamber 15 . In this way the steam reformer 1 performs an automatic matching to the load.
  • the losses of the reformate which can be affected are respectively proportional Delta T w (Delta T w is the difference between wall temperature and ambient temperature), Delta T 2 and Delta T R (see FIG. 2 ). They are furthermore a function of the excess steam in the reformate, which is necessary for soot-free reforming and the shift reaction.
  • the novel compact steam reformer 1 combines in one device the steam reformation of natural gas or other fuel, including subsequent cleaning of CO. Controlled catalytic CO cleaning is achieved by careful temperature control at the follow-up reactor 37 , 39 , 39 a. Temperature control is made possible by means of pressure-controlled operation of the evaporator 24 .

Abstract

The novel compact steam reformer (1) combines in one device the steam reformation of natural gas or other fuel, including subsequent cleaning of CO. Controlled catalytic CO cleaning is achieved by careful temperature control at the follow-up reactor (37, 39, 39 a). Temperature control is made possible by means of pressure-controlled operation of the evaporator (24).

Description

    CROSS-REFERENCE TO RELATED APPLICATION
  • This is a continuation-in-part application of international application PCT/EP2005/002194 filed Mar. 2, 2005, and claiming the priority of German application 10 2004 010 910.9 filed Mar. 6, 2004.
  • BACKGROUND OF THE INVENTION
  • The invention relates to a compact steam reformer and a method for steam reformation.
  • In the course of steam reforming hydrocarbons for the generation of hydrogen, the material flow for gas generation and the material flow for heating are kept separately in contrast to auto-thermal reforming. In this way the dilution of the hydrogen with nitrogen from the combustion air is avoided during steam reforming.
  • A compact steam reformer is known from DE 101 19 083 A1, in which the process water is essentially evaporated by means of the reformate to be cooled. The waste heat from the combustion is recovered by pre-warming the air. NOx formation is avoided by employing the flameless oxidation process. This reformer permits a rapid output regulation and has a degree of effectiveness of up to approximately 80%.
  • A similar reformer is known from WO 02/085781, which is optimized in respect to its exterior insulation.
  • These reformers meet the intended expectations. However, there is the desire for further improvements in regard to the simplification of the process regulation and the efficiency of the heat recovery. Moreover, the reformate must be relieved as much as possible of the addition of CO. This must take place so completely that downstream connected CO-sensitive fuel cells are not damaged.
  • It is known from EP 1 031 374 A2 to place the CO containing process gas into a so-called CO oxidator, which is simultaneously used as a reformate cooler. Cooling is achieved by evaporating the inflowing process gas in an evaporator.
  • Based on the foregoing, it is the object of the invention to improve the compact steam reformer mentioned at the outset in regard to the conduct of the process and the efficiency of the heat recovery.
  • This object is attained by means of the compact steam reformer in accordance with the invention as hereinafter described.
  • SUMMARY OF THE INVENTION
  • The novel compact steam reformer (1) combines in one device the steam reformation of natural gas or other fuel, including subsequent cleaning of CO. Controlled catalytic CO cleaning is achieved by careful temperature control at the follow-up reactor (37, 39, 39 a). Temperature control is made possible by means of pressure-controlled operation of the evaporator (24).
  • The compact steam reformer in accordance with the invention has a reactor which is heated by means of a burner. A preheating device with a high rate of heat recovery is assigned to the burner. This increases the efficiency of the reforming process. The reformer furthermore has a follow-up reactor, which is designed for performing a shift reaction, follow-up oxidation and/or methane generation from the carbon monoxide portions contained in the raw reformate. The follow-up reactor is in a heat-exchanging connection with a pipe evaporator, which maintains the temperature of the follow-up reactor at a fixed level in a controlled manner. By means of this, the desired selectivity of the follow-up reaction is maintained, even in case of a load change. The pipe evaporator causes the evening-out of the temperature in the follow-up reactor in regard to time, as well as in regard to space. The flow of material in the pipe evaporator causes a heat transport in the follow-up reactor, so that the latter can be rapidly adapted to a load change. This applies in particular if the pipe evaporator and the follow-up reactor operate in accordance with a co-current flow.
  • By means of the determination of the evaporator temperature, the temperature of the follow-up reactor is simultaneously fixed within such narrow limits that the CO content can be reduced to values of less than 50 ppm. Because of this, catalytic follow-up treatment, filtering or other follow-up treatment of the process gas becomes superfluous. The gas generated by the compact steam reformer can be directly conducted to hydrogen fuel cells.
  • The temperature of the follow-up reactor can be set in the simplest way by the regulation of the steam pressure. The steam generation temperature for all operational states is simultaneously fixed, along with the steam pressure. Thus, the close thermal connection between the follow-up reactor and the pressure-regulated evaporator, for example by means of the embodiment of the pipe evaporator as a pipe coil and the arrangement of possible catalyzers in the spaces between the pipes, creates favorable conditions for the generation of low-CO hydrogen.
  • The compact steam reformer can have a jet pump connected to the pipe evaporator or other evaporator, which generates a fuel—steam mixture of a preselected composition and feeds the reactor. This provides the basis for a particularly simple control of the compact steam reformer by means of control techniques. For example, the amount of steam is controlled by an appropriate metering of feed water amounts. The amount of fuel supplied to the reformer for reforming need not be separately controlled and is instead metered in by the jet pump.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • For a better understanding of the invention reference may be made to the accompanying exemplary embodiments of the invention illustrated in the drawings, in which:
  • FIG. 1 is a compact steam reformer with an attached fuel cell in a schematic representation;
  • FIG. 2 is the temperature profile of the process gases in the form of a diagram;
  • FIG. 3 is the temperature profile of the heating gases in the form of a diagram; and,
  • FIG. 4 is the compact steam reformer in schematic longitudinal section with the allocation of its work zones to the diagrams in accordance with FIGS. 2 and 3.
  • DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • A steam reformer 1 is represented in longitudinal section in FIG. 1. It has an outer shell 2 of a length L and circular cross section of a diameter D. It can be cylindrical, or also stepped in the form of several cylinders. All connectors 3 are preferably conducted through its upper end 4.
  • A reformer pipe 5, closed at the bottom, is arranged concentrically inside the shell 2 and at a distance from it. The annular space provided between the shell 2 and the reformer pipe 5 is filled with an insulating material 6 for thermal insulation. A feed line 7 for a mixture of fuel and steam leads from the upper end 4, extending initially straight and then downward by means of turns through the insulating material 6 to a feed connector 8 at the lower end of the reformer pipe 5. The lower, cup-shaped end of the latter constitutes the outer shell of a reactor 9 for performing the actual reforming process. Toward the inside, the reactor 9 is delimited by an inner reformer pipe 11, which is closed off in a cup shape at the bottom and is maintained on the end 4 at the top. A catalyzer 12 for the reforming process is arranged in the cup-shaped annular space between the lower end of the inner reformer pipe 11 and the lower end of the outer reformer pipe 5. Preferably the reformer pipe 11 is provided with ribs 13, 14 on the inside as well as on the outside, which are used for heat transfer between the catalyzer 12 and a combustion chamber 15, which is enclosed by the reformer pipe 11. A burner 16 is assigned to the combustion chamber and is used for heating the catalyzer 12 and is designed to create a flameless oxidation of the fuel introduced into the combustion chamber 15. A number of gas and air nozzles 17, 18 is provided for this purpose, which are arranged, aligned in the same direction, in a ring and create a large-volume circulation. A hollow-cylindrical guide body 19, which is arranged concentrically with the ring of nozzles can assist the large-volume circulation, which is indicated by arrows in FIG. 1.
  • The gas nozzles 17, as well as the air nozzles 18, are fed via a preheating arrangement 20, which utilizes waste heat. Parts of this are lines 21, 22, which are conducted in the form of coils through an exhaust gas conduit 23 formed inside the upper part of the reformer pipe 11. In this way the combustion gas supplied to the combustion chamber 15, as well as the supplied air, are preheated. A high recouperation degree, and therefore cool exhaust gas, is achieved. Preferably (1-Delta T2/Delta T1)>greater than 0.8, wherein Delta T1 is the exhaust gas difference between the inlet and outlet of the exhaust gas conduit 23 of the preheating arrangement 20, and Delta T2 is the difference between the exhaust gas temperature at the outlet and the fresh air temperature at the outlet. (1-Delta T2/Delta T1) is at least greater than 0.5.
  • An ignition burner Z or an electric heating device can be centrally provided, which are used for preheating the combustion chamber 15 until the start of the flameless oxidation.
  • The steam reformer 1 so far described contains a steam generator 24 arranged in the annular space 10 between the outer recouperation pipe 5 and the inner recouperation pipe 11 and is coupled with them in a heat-technological manner. Preferably the steam generator 24 is constituted by a pipe coil, which is divided into several sections and is arranged concentrically in respect to the preheating device. A pipe 25 is arranged in-between, which encloses a further annular space 26 together with the inner reformer pipe 11. This space is filled with an insulating material 27 for the thermal insulation of the exhaust gas conduit 23 from the reformate conduit, which is formed between the outer reformer pipe 5 and the pipe 25 through the annular space 10.
  • The steam generator 24 has a feedwater connector 28, starting from which a first pipe coil section 29 leads through the reformate conduit, which terminates at a reformate outlet 31. The pipe coil section 29 constitutes a water/reformate counterflow radiator operating in a counterflow manner.
  • The pipe coil 29 leads to a bridging pipe 32, which leads through the space 26 in the axial direction. It then changes back into the outer annular space 10 constituting the reformat conduit, and is continued there as the pipe coil section 33. It constitutes a water heater and simultaneously a reformate shock cooler (quench cooler, section A in FIGS. 3 and 5). A gas-permeable annular insulating body 34 is arranged between the pipe coil section 33 and the catalyzer 12, which prevents overheating of the steam generator 24 when there is no load, i.e. in case of a feedwater flow-through of zero or close to zero.
  • A further pipe coil section 35 follows the pipe coil section 33 and consists of several coils 36, 38 (section B in FIGS. 3 and 5). These coils 36, 38 have been embedded in a catalyzer, which also fills spaces between coils and constitutes a follow-up reactor. Here, the first coils 36 have been embedded, for example, in a CO-shift catalyzer 37. In the present exemplary embodiment the subsequent coils 38 (section C in FIGS. 3 and 5) have been embedded in a methane-generating catalyst 39. The catalysts 37, 39 can be attached to a suitable catalyst body, such as a woven wire device or the like, for example, or also deposited as loose bulk material between the coils 36, 38, or can be directly formed on the ribs of an evaporator embodied as a ribbed pipe.
  • In this way the evaporator 24 is divided into three sections A, B, C, namely the pipe coil section 33 for the at least partial evaporation of the water and shock cooling of the reformats, as well as the sections constituted by the coils 36 and 38, in which the further, to a large extent complete evaporation of the water is provided by heat exchange with the respective catalyzers 37, 39. The catalysts 37, 39 constitute the two-stage follow-up reactor.
  • The outlet of the evaporator 24 is connected via an ascending pipe 41 with a pressure-control valve 42, which maintains the pressure in the evaporator 24 constant, regardless of the flow through it. The steam emitted by the pressure-control valve 42 is conducted to the propellant nozzle connector 43 of a jet pump 44, whose suction connector 45 is connected to a fuel feed line. Its outlet feeds a mixture of steam and fuel to the feed line 7.
  • The feedwater connector 28 is provided with feedwater by a feedwater pump 46. The latter is controlled or regulated by a control device 47 on the basis of a temperature of the catalyzer 12 detected by means of a temperature sensor 48 in such a way, that the temperature of the catalyzer 12 is kept constant. Since the air requirement for the burner and the fuel cell are proportional to the energy supply PCH4, and therefore the feedwater temperature, the regulation ratio of the air blower 49 can track in a simple manner the regulation ratio of the feedwater pump 46, which is specified by the control device 47.
  • Air and combustion gas are supplied via the lines 21, 22. The residue gas from the anode of a fuel cell can be used as the combustion gas.
  • The reformate is conducted to an anode input of a fuel cell 52. Residue gas generated by the anode is conducted via a line 53 to the preheating arrangement 20. The blower 49 conveys air to the cathode of the fuel cell and to the preheating arrangement 20.
  • The steam reformer so far described operates as follows: Reference is made to FIGS. 2 to 4. Here, by means of a branch I of a curve, FIG. 3 illustrates the temperature of the gases supplied via the lines 21, 22, namely air and combustion gas. The branch II of the curve illustrates the exhaust gas temperature of the exhaust gas conducted out in counterflow. The represented temperatures reflect the temperature profile in the steam reformer 1 illustrated in FIG. 4, in particular in its recouperator. The loop-shaped branch III of the curve in FIG. 3 represents the temperature in the combustion chamber 15 in the course of the flameless oxidation. As represented, the gas performs several revolutions through the combustion chamber 15. As can be noted, it is possible at an exhaust gas temperature of, for example, 150° C., to attain an air and gas preheating up to approximately 800° C.
  • The curve in FIG. 2 represents the temperature profile of the gas to be reformed and already reformed. The branch IV of the curve indicates the heating of the feedwater in the pipe coil section 29, which is simultaneously a feedwater preheater and a water reformate counterflow cooler. Now the feedwater, which is under pressure and preheated, is conducted to the evaporator 24 at a temperature of slightly above 100° C. Initially, this is symbolized by the lower horizontal branch V of the curve. The preheated feedwater enters the evaporator at a point VI. It is brought to the evaporation temperature (curve VIII) in the pipe coil section 33, and then passes through the entire evaporator 24, in which it slowly evaporates. In the course of this it retains its evaporation temperature of 200° C., for example, as illustrated by the horizontal branch VIII of the curve. In the same way as a heating pipe, the pipe evaporator 24 sets a uniform temperature for the follow-up reactor. The evaporation temperature Ts is not exceeded. The size of the evaporator temperature is set by means of the evaporator pressure at the pressure-control valve 42.
  • The temperature profile in accordance with FIG. 2 is also maintained within narrow limits, even in case of load changes, in particular in the last stage. The selectivity of the follow-up reaction is maintained in this way. The temperature setting in the last follow-up reactor stage is here effected solely by pressure control.
  • From the evaporator 24, the generated steam reaches the jet pump 44. The latter fixes the steam/fuel ratio by means of its ratio between the propellant nozzle diameter and the mixing nozzle diameter. The jet pump 44 aspirates the desired amount of fuel via its suction connector 45 and mixes it with steam. In the process the steam temperature initially slightly drops (FIG. 2, branch XI of the curve), wherein the temperature of the admixed combustion gas suddenly rises (branch X of the curve). Then the temperature slowly rises until the feed connector 8 is reached (branch XI of the curve). In the catalyzer 12 the temperature of the curve continues to increase in accordance with the branch XII until it reaches the temperature TR, which has been detected by the temperature sensor 49 and is constantly regulated by metering in feedwater. The reformate generated by the catalyzer 12 leaves the reactor 9 at this temperature. When encountering the first section of the evaporator 24 (pipe coil section 33), the reformate is shock-cooled (FIG. 2, branch XIII of the curve) as section A.
  • Thereafter, the cooled reformate reaches the catalysts 37 and 39. There, a follow-up reaction for CO conversion takes place. The precise temperature control prevents too great a methane generation, in particular of the existing CO2 portions.
  • The steam reformer 1 so far described operates inherently stably. An increased reduction of the electrical output Pe1 worsens the caloric value of the residue gas from the anode. Thus, if the temperature at the temperature sensor 49 drops, the control device increases the feedwater conveyance and therefore the steam generation and the reformate generation. The resultant increase of residue gas from the anode increases the burner output in the combustion chamber 15. In this way the steam reformer 1 performs an automatic matching to the load.
  • An actual embodied steam reformer 1 has attained the following characteristic values: 100 ( V × Hu ) hydrogen eta R = A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o in % ( V × Hu ) process gas + ( V × Hu ) heating gas V [ m 3 / h ] - volume flow in standard state Hu [ kWh / m 3 ] - caloric value
    Efficiency of the conversion into hydrogen when heating the reformer with residue gas from the anode: 100 ( V × Hu ) hydrogen * eta R = A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o A o in % ( V × Hu ) process gas * hydrogen converted in the fuel cell ( typically 75 % )
  • Example of the novel reformer:
    • -Exterior dimensions: L=0.6 m, D=0.3 m -Process gas: 1 m3/h natural gas of caloric value of 10 kWh/m3 -Water: 2.5 kg/h at 15 bar (=3 m3/h steam, S/C=3) -Heating gas: 0.41 m3/h natural gas of caloric value of 10 kWh/m3 -Reformate: 4 m3/H2 of caloric value of 3 kWh/m3 -Efficiency etaR=85%
      When heating with residue gas from anode: (25% of H2 from the reformate, includes CH4 formed during methane generation)
    • -Available hydrogen: 2.7 m3/h of caloric value of 3 kWh/m3 -Efficiency etaR=81%
  • The losses of the reformate which can be affected are respectively proportional Delta Tw (Delta Tw is the difference between wall temperature and ambient temperature), Delta T2 and Delta TR (see FIG. 2). They are furthermore a function of the excess steam in the reformate, which is necessary for soot-free reforming and the shift reaction.
  • The novel compact steam reformer 1 combines in one device the steam reformation of natural gas or other fuel, including subsequent cleaning of CO. Controlled catalytic CO cleaning is achieved by careful temperature control at the follow-up reactor 37, 39, 39 a. Temperature control is made possible by means of pressure-controlled operation of the evaporator 24.

Claims (19)

1. A compact steam reformer (1) comprising,
a burner (16),
a reactor (9) which is heated by the burner (16) and is used for generating reformate from fuel and H2O steam,
a preheating arrangement (20) for preheating at least one of supplied air and supplied fuel while recouping exhaust gas heat, which is connected to the burner (16) and whose heat recouping quotient (Delta T1/Delta T2) is greater than 0.5,
an annular chamber (10) surrounding the preheating arrangement (20), through which reformate flows and which is thermally insulated toward the exterior,
a pipe evaporator (24) used for the generation of H2O steam under pressure and arranged in the annular chamber (10),
a follow-up reactor (37, 39, 39 a) for the extensive removal of carbon monoxide portions of the created reformate, which is also arranged in the annular chamber and is in thermal connection with the pipe evaporator (24) through which water flows.
2. The compact steam reformer of claim 1, wherein the reformate and water flow through the follow-up reactor (37, 39, 39 a) and the pipe evaporator (24) in the same flow direction.
3. The compact steam reformer of claim 1, wherein a water/reformate counterflow cooler (29) is connected to the inlet side of the pipe evaporator (24) and the outlet side of the follow-up reactor (37, 39, 39 a).
4. The compact steam reformer of claim 1, wherein the follow-up reactor (37, 39, 39 a) contains at least one of a shift catalyzer (37) and a methane-generating catalyzer (39) and a follow-up oxidation catalyzer (39 a).
5. The compact steam reformer of claim 1, wherein the pipe evaporator (24) is a pressure-proof pipe coil, having coil spaces in which the follow-up reactor (37, 39, 39 a) for encouraging the follow-up reaction is arranged.
6. The compact steam reformer of claim 1, wherein the pipe evaporator (24) is a pressure-proof ribbed pipe.
7. The compact steam reformer of claim 1, wherein a pressure regulator (42) is connected to the outlet of the pipe evaporator (24).
8. The compact steam reformer of claim 7, wherein the pressure regulator (42) is adjusted to such a pressure that the evaporation temperature of the water in the pipe evaporator (24) is set to a temperature between 130° C. and 280° C.
9. The compact steam reformer of claim 1, wherein the flow of material in the pipe evaporator (24) contains a liquid phase, in the area which is in thermal connection with the follow-up reactor (37, 39, 39 a).
10. The compact steam reformer of claim 1, further including a jet pump (44) connected to the pipe evaporator (24), the jet pump (44) for adding fuel by suction and for generating H2O steam/fuel mixture for feeding the reactor (9).
11. The compact steam reformer of claim 10, wherein the jet pump (44) is an unregulated jet pump.
12. The compact steam reformer of claim 1, wherein the reactor (9) is connected with a temperature sensor (48), for affecting the feedwater supply of the pipe evaporator (24) in such a way that the feedwater supply is increased if the temperature drops, and vice versa.
13. The compact steam reformer of claim 12, wherein the temperature sensor (48) controls a blower (49) for supplying the burner (16) with combustion air.
14. The compact steam reformer of claim 1, wherein the burner (16) is at least partially supplied with residue gas from the anode of a connected fuel cell (52).
15. A method for steam reforming of fuels by means of a steam reformer having an evaporator (24) for generating H2O steam under pressure and a jet pump (44) connected to the evaporator (24), the method comprises generating steam in the evaporator (24) and supplying the steam to the jet pump (44) as a propellant, and adding fuel by suction whereby an H2O steam/fuel mixture is generated for feeding a reactor (9).
16. The method of claim 15, further comprising heating the evaporator (24) by thermal contact with a follow-up reactor (37, 39, 39 a), whereby extensive removal of carbon monoxide portions of the generated reformate is accomplished.
17. The method of claim 15, further comprising regulating the pressure of the evaporator (24) for the operation of the evaporator (24) to take place.
18. The method of claim 17, wherein the evaporator pressure is maintained constant during the operation of the evaporator (24).
19. The method of claim 15, further comprising regulating the amount of feedwater being fed to the evaporator (24), whereby the output regulation of evaporation (24) is accomplished.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090191436A1 (en) * 2006-10-05 2009-07-30 Wunning Joachim A Fuel cell system
WO2011080781A1 (en) 2009-12-30 2011-07-07 Hysytech S.R.L. Endothermic reaction unit and steam reforming device comprising this reaction unit
EP2534096A2 (en) * 2010-02-13 2012-12-19 McAlister Technologies, LLC Chemical processes and reactors for efficiently producing hydrogen fuels and structural materials, and associated systems and methods
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US10888833B2 (en) 2016-03-23 2021-01-12 Karlsruher Institut Fuer Technologie Reactor for producing synthesis gas
US10899612B2 (en) * 2016-11-14 2021-01-26 Korea Institute Of Energy Research Hydrogen production reactor including carbon monoxide removing unit
US11480364B2 (en) * 2017-11-28 2022-10-25 Anderson Industries, Llc Flameless heater system to generate heat and humidity
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Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100599735B1 (en) 2004-11-29 2006-07-12 삼성에스디아이 주식회사 Fuel cell system and reformer
JP2007091584A (en) 2005-09-27 2007-04-12 Samsung Sdi Co Ltd Fuel reforming apparatus
DE102006039039A1 (en) * 2006-05-23 2007-11-29 Zentrum für Brennstoffzellen-Technik GmbH Heating of a catalyst stage mounted downstream of a reformer, comprises feeding of air as heat transfer medium into the reformer through supply line, heating the fed medium by heater and thermally coupling the heated up medium in the stage
JP5130684B2 (en) * 2006-09-27 2013-01-30 カシオ計算機株式会社 Reaction apparatus and electronic equipment
ATE470109T1 (en) 2007-05-23 2010-06-15 Ws Waermeprozesstechnik Gmbh RECUPERATOR BURNER WITH FLATTENED HEAT EXCHANGER TUBES
US9188086B2 (en) 2008-01-07 2015-11-17 Mcalister Technologies, Llc Coupled thermochemical reactors and engines, and associated systems and methods
US8441361B2 (en) 2010-02-13 2013-05-14 Mcallister Technologies, Llc Methods and apparatuses for detection of properties of fluid conveyance systems
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US9126831B2 (en) * 2010-03-31 2015-09-08 Council Of Scientific & Industrial Research Hydrogen/syngas generator with sampling ports
US8920732B2 (en) 2011-02-15 2014-12-30 Dcns Systems and methods for actively controlling steam-to-carbon ratio in hydrogen-producing fuel processing systems
DE102011013026A1 (en) 2011-03-04 2012-09-06 Dbi - Gastechnologisches Institut Ggmbh Freiberg Process and arrangement for steam reforming of hydrocarbon gases
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US8911703B2 (en) 2011-08-12 2014-12-16 Mcalister Technologies, Llc Reducing and/or harvesting drag energy from transport vehicles, including for chemical reactors, and associated systems and methods
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US8734546B2 (en) 2011-08-12 2014-05-27 Mcalister Technologies, Llc Geothermal energization of a non-combustion chemical reactor and associated systems and methods
US9522379B2 (en) 2011-08-12 2016-12-20 Mcalister Technologies, Llc Reducing and/or harvesting drag energy from transport vehicles, including for chemical reactors, and associated systems and methods
US9039327B2 (en) 2011-08-12 2015-05-26 Mcalister Technologies, Llc Systems and methods for collecting and processing permafrost gases, and for cooling permafrost
WO2014160301A1 (en) 2013-03-14 2014-10-02 Mcalister Technologies, Llc Method and apparatus for generating hydrogen from metal
US20150285534A1 (en) * 2014-04-02 2015-10-08 King Fahd University Of Petroleum And Minerals Solar collector with optimal profile for energy distribution on a tubular receiver
CN104226206A (en) * 2014-07-28 2014-12-24 河北新启元能源技术开发股份有限公司 Pressure difference reducing device using organic solvent to wash reactor
DE102016208843A1 (en) * 2016-05-23 2017-11-23 Siemens Aktiengesellschaft Reactor with a jet pump and method of increasing the pressure of a reactant with a jet pump
CN106025448A (en) * 2016-07-15 2016-10-12 郑州佛光发电设备有限公司 Liquid pipeline built-in compact type aluminum-air fuel cell monomer
CN106365118B (en) * 2016-11-15 2018-09-14 晋城市阿邦迪能源有限公司 Methanol steam reforming room with CO purifications and temp monitoring function
US11285003B2 (en) 2018-03-20 2022-03-29 Medtronic Vascular, Inc. Prolapse prevention device and methods of use thereof
US11026791B2 (en) 2018-03-20 2021-06-08 Medtronic Vascular, Inc. Flexible canopy valve repair systems and methods of use
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CN115650165A (en) * 2022-11-15 2023-01-31 中国科学院大连化学物理研究所 Fuel evaporation chamber structure used in cooperation with hydrogen production reformer of fuel cell

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5595833A (en) * 1994-02-19 1997-01-21 Rolls-Royce Plc Solid oxide fuel cell stack
US20020083829A1 (en) * 1996-10-30 2002-07-04 Edlund David J. Hydrogen purification membranes, components and fuel processing systems containing the same
US6641625B1 (en) * 1999-05-03 2003-11-04 Nuvera Fuel Cells, Inc. Integrated hydrocarbon reforming system and controls

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3745047A (en) * 1970-12-31 1973-07-10 United Aircraft Corp Proportional action electronic fuel control for fuel cells
JPS5981416A (en) * 1982-11-01 1984-05-11 Yoshimitsu Sumiyoshi Steam reforming method and device therefor
JPS6270202A (en) * 1985-09-19 1987-03-31 Fuji Electric Co Ltd Fuel reforming apparatus for fuel cell
JPH09241002A (en) * 1996-03-11 1997-09-16 Fuji Electric Co Ltd Fuel reformer for fuel cell power generator
ATE275529T1 (en) * 1996-06-28 2004-09-15 Matsushita Electric Works Ltd REFORMING DEVICE FOR PRODUCING A CRACKED GAS WITH REDUCED CO CONTENT.
US6126908A (en) * 1996-08-26 2000-10-03 Arthur D. Little, Inc. Method and apparatus for converting hydrocarbon fuel into hydrogen gas and carbon dioxide
US5997594A (en) * 1996-10-30 1999-12-07 Northwest Power Systems, Llc Steam reformer with internal hydrogen purification
JPH10223244A (en) * 1997-02-03 1998-08-21 Fuji Electric Co Ltd Fuel cell electricity generating apparatus
DE19721630C1 (en) * 1997-05-23 1999-02-11 Fraunhofer Ges Forschung Device for reforming hydrocarbons containing starting materials
EP1138096B1 (en) * 1998-10-14 2010-10-06 IdaTech, LLC Fuel processing system
DE19907665C2 (en) 1999-02-23 2003-07-31 Ballard Power Systems Device for utilizing heat generated during a catalytic reaction
EP1094031A4 (en) * 1999-04-20 2005-02-02 Tokyo Gas Co Ltd Single-pipe cylindrical reformer and operation method therefor
AU768496B2 (en) * 1999-05-03 2003-12-11 Nuvera Fuel Cells Autothermal reforming system with integrated shift beds, preferential oxidation reactor, auxiliary reactor, and system controls
DE19954871A1 (en) * 1999-09-07 2001-03-15 Caloric Anlagenbau Gmbh Hydrogen recovery from hydrocarbons involves steam reforming in presence of catalyst, separating hydrogen and recycling residual gas stream to reformer
JP3903710B2 (en) * 2000-07-25 2007-04-11 富士電機ホールディングス株式会社 Fuel reformer and polymer electrolyte fuel cell power generator using the same
DE10119083C1 (en) 2001-04-19 2002-11-28 Joachim Alfred Wuenning Compact steam reformer
JP2004059415A (en) * 2002-06-03 2004-02-26 Mitsubishi Heavy Ind Ltd Fuel reformer and fuel cell power generation system
JP2004031280A (en) * 2002-06-28 2004-01-29 Ebara Ballard Corp Fuel processing device, fuel cell power generation system, fuel processing method and fuel cell power generation method
JP4520100B2 (en) * 2003-03-20 2010-08-04 新日本石油株式会社 Hydrogen production apparatus and fuel cell system

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5595833A (en) * 1994-02-19 1997-01-21 Rolls-Royce Plc Solid oxide fuel cell stack
US20020083829A1 (en) * 1996-10-30 2002-07-04 Edlund David J. Hydrogen purification membranes, components and fuel processing systems containing the same
US6641625B1 (en) * 1999-05-03 2003-11-04 Nuvera Fuel Cells, Inc. Integrated hydrocarbon reforming system and controls

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090191436A1 (en) * 2006-10-05 2009-07-30 Wunning Joachim A Fuel cell system
US8313867B2 (en) 2006-10-05 2012-11-20 Ws Reformer Gmbh Fuel cell system
WO2011080781A1 (en) 2009-12-30 2011-07-07 Hysytech S.R.L. Endothermic reaction unit and steam reforming device comprising this reaction unit
EP2534096A2 (en) * 2010-02-13 2012-12-19 McAlister Technologies, LLC Chemical processes and reactors for efficiently producing hydrogen fuels and structural materials, and associated systems and methods
EP2534097A2 (en) * 2010-02-13 2012-12-19 McAlister Technologies, LLC Reactor vessels with pressure and heat transfer features for producing hydrogen-based fuels and structural elements, and associated systems and methods
EP2534097A4 (en) * 2010-02-13 2014-06-11 Mcalister Technologies Llc Reactor vessels with pressure and heat transfer features for producing hydrogen-based fuels and structural elements, and associated systems and methods
EP2534096A4 (en) * 2010-02-13 2014-06-11 Mcalister Technologies Llc Chemical processes and reactors for efficiently producing hydrogen fuels and structural materials, and associated systems and methods
US10888833B2 (en) 2016-03-23 2021-01-12 Karlsruher Institut Fuer Technologie Reactor for producing synthesis gas
US10899612B2 (en) * 2016-11-14 2021-01-26 Korea Institute Of Energy Research Hydrogen production reactor including carbon monoxide removing unit
US11480364B2 (en) * 2017-11-28 2022-10-25 Anderson Industries, Llc Flameless heater system to generate heat and humidity
FR3129608A1 (en) * 2021-11-30 2023-06-02 Naval Group REFORMER STRUCTURE

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CN1980732A (en) 2007-06-13
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